EP1957600A1 - Adjuvant for controlling polishing selectivity and chemical mechanical polishing slurry comprising the same - Google Patents
Adjuvant for controlling polishing selectivity and chemical mechanical polishing slurry comprising the sameInfo
- Publication number
- EP1957600A1 EP1957600A1 EP06824023A EP06824023A EP1957600A1 EP 1957600 A1 EP1957600 A1 EP 1957600A1 EP 06824023 A EP06824023 A EP 06824023A EP 06824023 A EP06824023 A EP 06824023A EP 1957600 A1 EP1957600 A1 EP 1957600A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- adjuvant
- polyelectrolyte
- polishing selectivity
- controlling polishing
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 101
- 239000002002 slurry Substances 0.000 title claims abstract description 76
- 239000002671 adjuvant Substances 0.000 title claims abstract description 55
- 239000000126 substance Substances 0.000 title claims description 8
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 105
- 239000002801 charged material Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- -1 potassium tetrafluoroborate Chemical compound 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 2
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- PTMFUWGXPRYYMC-UHFFFAOYSA-N triethylazanium;formate Chemical compound OC=O.CCN(CC)CC PTMFUWGXPRYYMC-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 18
- 239000004065 semiconductor Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000007517 polishing process Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 50
- 229910052581 Si3N4 Inorganic materials 0.000 description 30
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 30
- 235000012431 wafers Nutrition 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000004377 microelectronic Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000293849 Cordylanthus Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910009111 xH2 O Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Definitions
- the present invention relates to an adjuvant for controlling polishing selectivity when polishing a cationically charged material and an anionically charged material simultaneously. Also, the present invention relates to CMP (chemical mechanical polishing) slurry comprising the same.
- CMP chemical mechanical polishing
- planarization processes used for manufacturing such microelectronic devices have become more and more important.
- multiple interconnection technique and multilayer stacking technique have generally been used for semiconductor wafers.
- non-planarization occurring after carrying out one of the above techniques causes many problems. Therefore, planarization processes are applied to various steps in a microelectronic device manufacturing process, so as to minimize irregularity on wafer surfaces.
- CMP chemical reagent known as CMP slurry
- CMP technique accomplishes planarization of a wafer surface by way of chemical and physical actions.
- CMP technique accomplishes planarization of a wafer surface by pressing the wafer surface against the polishing pad that rotates relative to the surface, and by supplying a chemically active slurry to the wafer surface having a pattern at the same time.
- One embodiment, to which CMP technique is applied, is STI (shallow trench
- the STI process has been recently developed so as to solve the problem occurring in the conventional LOCOS (local oxidation of silicon) processes and to make electric insulation between chips. This is because the conventional LOCOS processes cause the problem of a so-called Bird's Beak phenomenon, while minimum line width standard becomes more strict to a degree of 0.13 D or less.
- LOCOS local oxidation of silicon
- minimum line width standard becomes more strict to a degree of 0.13 D or less.
- relatively shallow trenches are formed, and such trenches are used in forming field regions for separating active regions on wafer surfaces.
- a pad silicon oxide (SiO ) layer 101 and a silicon nitride (SiN) layer 102 are formed successively on a semiconductor wafer.
- the insulating silicon oxide layer 104 and the SiN layer 102 show different removal rates due to their different chemical and physical properties.
- the SiN layer pattern may be removed non-uniformly depending on locations in a wafer during a CMP process. Therefore, the SiN layer has a variable thickness over the whole wafer. Particularly, this is a serious problem in the case of a semiconductor wafer that has a highly dense pattern simultaneously with a sparse pattern.
- a final structure having field regions has a level difference between active regions and field regions, resulting in reduction of the margin of subsequent steps for manufacturing a semiconductor device, and degradation of the quality of a transistor and a device.
- conventional CMP processes are problematic in that a SiN layer pattern with a uniform thickness cannot be obtained even after removing the oxide layer via a CMP process.
- the inventors of the present invention have recognized that when a poly electrolyte is used as an adjuvant that forms an adsorption layer on a cationically charged material during the simultaneous polishing of the cationically charged material and the an- ionically charged material to increase polishing selectivity of an anionically charged material, slurry dispersibility decreases and an agglomeration phenomenon occurs due to a great amount of the added polyelectrolyte, resulting in an increase in the particle diameter to a degree of 1 D or more and severe variations in particle size with time. Additionally, the inventors have also found that when a fluorine-based compound is used in combination with such adjuvants, variations in particle size and viscosity decrease. The present invention is based on these findings.
- an adjuvant for controlling polishing selectivity when polishing a cationically charged material simultaneously with an anionically charged material comprising: (a) a polyelectrolyte that forms an adsorption layer on the cationically charged material in order to increase the polishing selectivity of the anionically charged material; (b) a basic material; and (c) a fluorine-based compound.
- CMP slurry comprising the same adjuvant and abrasive particles is also provided.
- silicon oxide is anionically charged. Therefore, in order to increase the polishing selectivity of silicon oxide to silicon nitride, an anionically charged polymer, such as a polyelectrolyte, is adsorbed onto the cationically charged silicon nitride via electrostatic force, so that the cationically charged silicon nitride is prevented from being polished, and thus the anionically charged silicon oxide becomes more amenable to polishing. By doing so, it is possible to realize a polishing selectivity of an anionically charged material to a cationically charged material of 30: 1 or higher.
- an anionically charged polymer such as a polyelectrolyte
- the anionically charged polymer if the molecular weight of the anionically charged polymer is too low, the polymer is adsorbed onto the structure of a cationically charged material sparsely or in the form of a thin adsorption layer. Therefore, it is not possible to protect the structure of the cationically charged material sufficiently from the polishing work.
- the anionically charged polymer has a high molecular weight. However, if the molecular weight is too high, the polymer is partially adsorbed onto abrasive particles via van der waals force to cause agglomeration of the particles. Furthermore, such agglomerated particles may entail scratches during a CMP process.
- polishing selectivity when a polyelectrolyte is used as an adjuvant for controlling polishing selectivity, polishing selectivity may be improved, but the overall polishing rate may be degraded.
- the present invention is characterized in that a fluorine-based compound is used in combination with a polyelectrolyte as an adjuvant for controlling polishing selectivity in order to obtain polishing slurry that has a uniform particle size and is stable against viscosity variations caused by external force, to minimize generation of microscratch during a polishing process, and to improve the productivity.
- the polyelectrolyte that may be used in the present invention preferably includes a linear polyelectrolyte having a weight average molecular weight of 2,000 ⁇ 50,000, a graft type polyelectrolyte that has a weight average molecular weight of 1,000 ⁇ 20,000 and comprises a backbone and a side chain, or a mixture thereof.
- a linear polyelectrolyte having a controlled molecular weight In order to maximize the electrostatic adsorption of the anionically charged polymer such as polyelectrolyte onto the structure of the cationically charged material, as well as to minimize the adsorption due to the van der waals force, a linear polyelectrolyte having a controlled molecular weight, a graft type polyelectrolyte containing a backbone and a side chain, or a mixture thereof is used.
- a backbone chain length of the graft type polyelectrolyte is shorter than the chain length of the linear polyelectrolyte, so that the graft type polyelectrolyte can minimize an agglomeration phenomenon.
- the graft type polyelectrolyte which has the side chain grafted to the backbone, can form an adsorption layer on the structure of the cationically charged material with higher polymer density per unit area, to a larger thickness, in proportion to the length of the side chain (see FlG. 2).
- a graft type polyelectrolyte When using a graft type polyelectrolyte, it can be adsorbed selectively on the structure of a cationically charged material to a high thickness with no need for increasing the molecular weight.
- the structure of the cationically charged material having an absorption layer formed by electrostatic force can be protected from being polished, so that polishing selectivity of the structure of the structure of an anionically charged material (e.g. silicon oxide) to the structure of a cationically charged material (e.g. silicon nitride) may be increased.
- an anionically charged material e.g. silicon oxide
- a cationically charged material e.g. silicon nitride
- a polishing selectivity required in a CMP process is 30: 1 or higher.
- polishing selectivity of the structure of an anionically charged material (e.g. silicon oxide) to the structure of a cationically charged material (e.g. silicon nitride) may be 30:1 or higher.
- polishing selectivity of the structure of an anionically charged material (e.g. silicon oxide) to the structure of a cationically charged material (e.g. silicon nitride) may be higher than the above polishing selectivity obtained by using the linear polyelectrolyte.
- the polishing selectivity in a range from 50:1 to 100:1.
- the linear polyelectrolyte used in the present invention is a compound containing a carboxyl group, and particular examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, or the like.
- Commercially available linear polymer materials include Cerasprese 5468 available from Korea Sannopco Co. and linear polymers available from Aldrich Co., or the like.
- the linear polyelectrolyte preferably has a weight average molecular weight of
- the linear polyelectrolyte has a weight average molecular weight less than 2,000, the polishing rate of a silicon nitride layer increases, resulting in a drop in polishing selectivity. On the other hand, if the linear polyelectrolyte has a weight average molecular weight grater than 50,000, the polishing rate of a silicon oxide layer decreases.
- the graft type polyelectrolyte that may be used in the present invention is comprised of a backbone 200 and a side chain 201.
- the graft type polyelectrolyte has a weight average molecular weight of 1,000 ⁇ 20,000, and preferably of 3,000 ⁇ 15,000. If the graft type polyelectrolyte has a weight average molecular weight of less than 1,000 or of greater than 20,000, a stable slurry composition cannot be obtained. Additionally, if the polyelectrolyte has a weight average molecular weight of greater than 20,000, abrasive particles are agglomerated. Moreover, in the latter case, the polyelectrolyte is adsorbed onto the structure of the anionically charged material (e.g. silicon oxide) as well as onto the structure of the cationically charged material (e.g.
- the anionically charged material e.g. silicon oxide
- the side chain in the graft type polyelectrolyte preferably has a length corresponding to a molecular weight of 500 ⁇ 2,000, and the backbone in the graft type polyelectrolyte has a length corresponding to a molecular weight of 500 ⁇ 15,000. If the length of the side chain is too short, the polyelectrolyte cannot perform the protection function sufficiently due to the small coating thickness. On the other hand, if the length of the side chain is too long, agglomeration of particles may occur. Additionally, if the length of the backbone is too short, the polyelectrolyte results in poor adsorption. On the other hand, if the length of the backbone is too long, agglomeration of particles may occur.
- the backbone of the polyelectrolyte serves as a major site participating in the electrostatic adsorption.
- the backbone preferably contains a large amount of anionic units for the purpose of adsorption onto the structure of the cationically charged material.
- anionic units comprise functional groups such as a carboxylic acid group as a part.
- the side chain affects the electrostatic adsorption to a lower degree as compared to the backbone. Hence, it is not necessary for the side chain to be anionically charged. However, the side chain should not be cationic.
- the side chain mainly serves to form the adsorption coating layer with a larger thickness.
- the side chain of the graft type polyelectrolyte comprises a macrounit derived from the polymerization or copolymerization of a hydroxyl group-, carboxyl group- and/or sulfonic acid group-containing ethylenically unsaturated monomer(s).
- the backbone of the graft type polyelectrolyte comprises a unit derived from a carboxyl group-containing ethylenically unsaturated monomer.
- slurry for polishing uses water as a dispersion medium.
- the graft type polyelectrolyte is dissolved in water.
- the macrounit forming the side chain of the graft type polyelectrolyte is hydrophilic, and preferably contains units derived from monomers with high affinity to water (for example, hydroxyl group-, carboxyl group-, and/or sulfonic acid group- containing ethylenically unsaturated monomers).
- the macrounit is a short chain polymer, and is derived from a macromonomer polymerized from 8 ⁇ 16 sub- monomers and end-capped with a functional group. Because if the side chain comprising the macrounit is too long, an agglomeration phenomenon occurs and if the side chain comprising the macrounit is too short, the polyelectrolyte cannot perform the protection function.
- the graft type polyelectrolyte used in the present invention may be prepared by using the method as disclosed in Korean Laid-Open Patent No. 2005-0113758, the entire content of which is incorporated herein by reference.
- main monomers used for forming the graft type polyelectrolyte include carboxylic acids such as acrylic acid.
- carboxylic acids such as acrylic acid.
- the reaction mixture for forming the polymer cannot be agitated due to the formation of the polymer and its high viscosity.
- R ' is a hydrogen atom or methyl
- R O is a C2 ⁇ C4 oxyalkylene or a combination thereof, and may be added
- R 3 is a Cl ⁇ C4 alkyl
- the alkoxypolyalkylene glycol mono(meth)acrylate monomer is N-(meth)-acrylate monomer
- the polyelectrolyte in an amount of 10 ⁇ 50 wt%. If the monomer is contained in an amount less than 10 wt%, it is difficult to obtain high selectivity, which is otherwise obtained from a graft type polyelectrolyte. If the monomer is contained in an amount higher than 50 wt%, a final slurry composition using a high-selectivity additive comprising the same may show the problem of increased air bubble generation.
- 50,000 and the graft type polyelectrolyte having a weight average molecular weight of 1,000 ⁇ 20,000 each may be used alone, or in combination.
- each of the linear polyelectrolyte, the graft type polyelectrolyte and a mixture thereof may be converted into a polyelectrolyte salt by using a basic material in an aqueous phase.
- the scope of the present invention may include polyelectrolyte types other than a polyelectrolyte salt.
- the polyelectrolyte salt according to the present invention has a pH of 4.5 ⁇ 8.8, and preferably of 6.0 ⁇ 8.0. If the pH is less than 4.5 or greater than 8.8, it is not possible to obtain a sufficient level of polishing selectivity.
- the fluorine-based compound used in the present invention inhibits abrasive particles from agglomerating due to the polyelectrolyte, so that the particles maintain a uniform size and a uniform variation in viscosity caused by external force.
- the fulorine-based compound improves the uniformity during a polishing process and minimizes generation of microscratch.
- the fluorine-based compound increases the polishing rate of an oxide layer.
- the fluorine-based compounds that may be used in the present invention include fluorides, acids including hydrofluoric acid, fluoropolymers, or organic/inorganic fluorine-containing acid. Particular examples thereof include hydrofluoric acid (HF), potassium fluoride (KF), sodium fluoride (NaF), fluorosilicic acid (H SiF ),
- the fluorine-based compound is used in an amount of 0.01 ⁇ 5.0 parts by weight per 100 parts by weight of the polyelectrolyte. If the fluorine-based compound is used in an amount less than 0.01 parts by weight, it is not possible to obtain a uniform particle size of CMP slurry and uniform variations in viscosity of CMP slurry to a desired degree. If the fluorine-based compound is used in an amount greater than 5.0 parts by weight, microscratches increase because the compound adversely affects dispersion stability and storage stability of CMP slurry.
- CMP slurry which comprises: (a) the adjuvant as described above; (b) abrasive particles; and (c) water.
- the abrasive particles are used in the CMP slurry in an amount of 0.1 ⁇ 10 wt%. If the amount is less than 0.1 wt%, high removal rate of oxide layer cannot be achieved sufficiently. On the other hand, if the amount is greater than 10 wt%, the slurry shows poor stability.
- nano-sized ceramic abrasive particles such as silica, alumina, zirconia, titania or cerium oxide particles may be used. Preferably, cerium oxide particles are used.
- the CMP slurry may be prepared by using the polyelectrolyte salt dissolved in a solvent (e.g. water), and the abrasive particles dispersed in a dispersion medium (e.g. water).
- a solvent e.g. water
- a dispersion medium e.g. water
- the aqueous solution of the polyelectrolyte salt has a concentration of 3 ⁇ 3.5 wt%
- the water dispersion of the abrasive particles has a concentration of 4 ⁇ 6 wt%.
- FIG. 2 is a schematic view showing the structure of a graft type polyelectrolyte according to a preferred embodiment of the present invention.
- an aqueous monomer solution containing 300 parts by weight of acrylic acid mixed with 250 parts by weight of distilled water and 90 parts by weight of an aqueous solution containing 9.7 wt% of ammonium peroxide as an initiator were added dropwise over 3 hours. After the completion of the addition, the reaction mixture was aged while maintaining the temperature at 80 °C for 2 hours to complete the polymerization.
- the linear polyelectrolyte had a relative molecular weight of 24166, a polydispersity index of 1.76 and a solid content of 40.72 wt%.
- polishing selectivity of CMP slurry and mixing the adjuvant composition, abrasive particle composition and water in a volume ratio of 1:3:3.
- the slurry composition was controlled to have a pH of 7.5-8.0.
- CMP slurry were provided in the same manner as described in Example 1, except that linear polyelectrolytes having different molecular weight characteristics as shown in the following Table 1 were used instead of the linear polyelectrolyte used in Example 1.
- the graft type polyelectrolyte had a weight average molecular weight of 17,896.
- An adjuvant composition for controlling polishing selectivity and CMP slurry were provided in the same manner as described in Example 1, except that a polyelectrolyte mixture containing 50 wt% of the linear polyelectrolyte obtained from Example 1 and 50 wt% of the graft type polyelectrolyte obtained from Example 6 was used instead of the linear polyelectrolyte used in Example 1.
- Microtrap UPA150 (Honeywell, USA).
- CMP slurry was mixed with each adjuvant composition for controlling polishing selectivity according to Examples 1 ⁇ 8 and Comparative Examples 1 ⁇ 8. Then, agglomerated particle size of the mixture was determined for 600 seconds at an interval of 120 seconds. Agglomerated particle size variance was determined as a difference between the highest value and the lowest value.
- Viscosity was measured by using ARES Rheometer (Rheometric
- shear modulus was fixed at 100, viscosity was measured for 600 seconds at an interval of 10 seconds, and viscosity variance was determined as a difference between the highest viscosity and the lowest viscosity.
- polishing quality was determined under the following conditions:
- CMP was carried out under the above conditions by using the CMP slurry obtained from Examples 1 ⁇ 8 and Comparative Examples 1 ⁇ 8 for 1 minute. Then, polishing rate and polishing selectivity were measured from a variance in thickness after polishing. The results are shown in the following Table 2.
- WIWNU Within Wafer Non-Uniformity - a value obtained by dividing the standard deviation in wafer thickness after polishing by the average wafer thickness. A lower WIWNU indicates a higher planarization degree.
- both the agglomerated particle size variance and the viscosity variance are very low, as compared to the examples using a linear polyelectrolyte alone.
- the resultant polishing slurry has excellent stability and minimizes generation of scratch.
- the adjuvant for controlling polishing selectivity of CMP slurry according to the present invention when the adjuvant for controlling polishing selectivity of CMP slurry according to the present invention is applied to a CMP process, it is possible to increase the polishing selectivity of a silicon oxide layer, to obtain a uniform particle size of CMP slurry, to stabilize variations in viscosity under an external force and to minimize generation of microscratches during a polishing process. Therefore, the adjuvant for CMP slurry according to the present invention can improve reliability and productivity during the fabrication of very large scale integrated semiconductors.
Abstract
Description
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PCT/KR2006/005317 WO2007067003A1 (en) | 2005-12-08 | 2006-12-08 | Adjuvant for controlling polishing selectivity and chemical mechanical polishing slurry comprising the same |
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WO2009104334A1 (en) * | 2008-02-18 | 2009-08-27 | Jsr株式会社 | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method |
KR101180401B1 (en) | 2009-09-23 | 2012-09-10 | 주식회사 엘지화학 | Slurry composition for chemical mechanical polishing and polishing method |
TWI431080B (en) | 2009-10-13 | 2014-03-21 | Lg Chemical Ltd | Slurry composition for chemical mechanical polishing and polishing method |
CN101857774B (en) * | 2010-06-01 | 2013-12-25 | 上海新安纳电子科技有限公司 | Polishing composition for improving chemical-mechanical polishing rate of silicon substrate and application thereof |
JP5696024B2 (en) * | 2011-11-09 | 2015-04-08 | 株式会社東芝 | Chemical planarization method and chemical planarization apparatus |
CN103146307B (en) * | 2013-03-28 | 2014-12-10 | 天津理工大学 | Nano polishing solution for chemical/mechanical polishing |
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JP6586799B2 (en) * | 2015-07-07 | 2019-10-09 | 日立化成株式会社 | Abrasive, abrasive set, and substrate polishing method |
KR102628333B1 (en) * | 2015-09-09 | 2024-01-22 | 가부시끼가이샤 레조낙 | Polishing liquid, polishing liquid set, and base polishing method |
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US8147711B2 (en) | 2012-04-03 |
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